Rh-Catalyzed Direct Decarbonylative Borylation of Carboxylic Acids.

Carboxylic acids are abundant, low cost and environmentally friendly, direct convert carboxylic acids into valued-added compounds are in high demand. Herein, we report a Rh(I) catalyzed direct decarbonylative borylation of aryl and alkyl carboxylic acid using TFFH as activator. This protocol features excellent functional-group tolerance and a broad substrate scope including natural product and drugs. A gram-scale decarbonylative borylation reaction of Probenecid is also presented. In addition, the utility of this strategy is highlighted by a one-pot decarbonylative borylation/ derivatization sequence.

Facile Synthesis of Alkylidene Phthalides by Rhodium-Catalyzed Domino C-H Acylation/Annulation of Benzamides with Aliphatic Carboxylic Acids.

The Rh-catalyzed ortho-C(sp2 )-H functionalization of 8-aminoquinoline-derived benzamides with aliphatic acyl fluorides generated in situ from the corresponding acids has been developed. This reaction initiated with 8-aminoquinoline-directed ortho-C(sp2 )-H acylation, which was accompanied by subsequent intramolecular nucleophilic acyl substitution of amide group to produce alkylidene phthalides This approach exhibits high stereo-selectivity for Z-isomer products, and tolerates a variety of functional groups as well as aliphatic carboxylic acids with diverse structural scaffolds.

N-Heterocyclic carbene-palladium(ii)-1-methylimidazole complex catalyzed direct C-H bond arylation of imidazo[1,2-a]pyridines with aryl chlorides.

We herein reported the N-heterocyclic carbene-palladium(ii)-1-methylimidazole complex catalyzed direct C-H bond arylation of imidazo[1,2-a]pyridines with aryl chlorides. Under suitable conditions, all reactions between various imidazo[1,2-a]pyridines and aryl chlorides worked well to give the desired C3-H arylated products in acceptable to high yields, giving a convenient and alternative method for the direct C-H bond arylation of imidazo[1,2-a]pyridines, using economic and easily available aryl chlorides as the arylating reagents.

A facile method for Rh-catalyzed decarbonylative ortho-C-H alkylation of (hetero)arenes with alkyl carboxylic acids.

A facile and effective method for Rh-catalyzed direct ortho-alkylation of C-H bonds in (hetero)arenes with commercially available carboxylic acids has been developed. This strategy was initiated by in situ conversion of carboxylic acids to anhydrides which, without isolation, underwent Rh-catalyzed direct decarbonylative cross-coupling of aryl carboxamides containing 8-aminoquinoline. The reaction proceeds with high regioselectivity and exhibits a broad substrate scope as well as functional group tolerance.

Rh-Catalyzed General Method for Directed C-H Functionalization via Decarbonylation of in-Situ-Generated Acid Fluorides from Carboxylic Acids.

A Rh-catalyzed decarbonylative C-H coupling of in-situ-generated acid fluorides with amide substrates bearing ortho-Csp2-H bonds has been developed. This method enables alkyl, aryl, and alkenyl carboxylic acids to undergo decarbonylative coupling with C-H bonds of (hetero)aromatic or alkenyl amides in generally good yields via the in situ conversion of carboxylic acids into acid fluorides and also allows for the functionalization of a series of structurally complex carboxyl-containing natural products and pharmaceuticals as well as pharmaceutical amide derivatives.